US4332940A - Process for the production of 2,3-cycloalkenopyridines - Google Patents

Process for the production of 2,3-cycloalkenopyridines Download PDF

Info

Publication number
US4332940A
US4332940A US05/830,983 US83098377A US4332940A US 4332940 A US4332940 A US 4332940A US 83098377 A US83098377 A US 83098377A US 4332940 A US4332940 A US 4332940A
Authority
US
United States
Prior art keywords
catalyst
cycloalkanone
oxide
isophorone
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/830,983
Inventor
Helmut Beschke
Heinz Friedrich
Heribert Offermanns
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Deutsche Gold und Silber Scheideanstalt
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Deutsche Gold und Silber Scheideanstalt filed Critical Deutsche Gold und Silber Scheideanstalt
Assigned to DEUTSCHE GOLD-UND SILBER-SCHEIDEANSTALT VORMALS ROESSLER reassignment DEUTSCHE GOLD-UND SILBER-SCHEIDEANSTALT VORMALS ROESSLER ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OFFERMANNS, HERIBERT, BESCHKE, HELMUT, FRIEDRICH, HEINZ
Application granted granted Critical
Publication of US4332940A publication Critical patent/US4332940A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems

Definitions

  • the invention is directed to a process for the production of 2,3-cycloalkenopyridines by the catalytic reaction of a cycloalkanone or cycloalkenone with an aliphatic oxo compound at elevated temperature.
  • the 2,3-cycloalkenopyridines are important intermediate products for the production of medicines, plant protective agents and synthetic resins.
  • cycloalkanones there can be used for example cyclobutanone, cyclopentadecanone, cyclohexadecanone, cyclooctadecanone, 3,5,5-trimethyl cyclohexanone, camphor, 1-decalone, 2-butyl cyclohexanone, 2-propyl cyclohexanone, 8-ketotricyclodecane, carvone, and especially cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclodecanone, cyclododecanone, 2-methyl cyclohexanone, 3-methyl cyclohexanone, 2,2,4-trimethyl cyclopentanone and menthone.
  • An example of a cycloalkenone is isophorone.
  • Suitable oxo compounds are for example, methacrolein, crotonaldehyde, methyl vinyl ketone, ethyl vinyl ketone, 3-penten-2-one, hexyl vinyl ketone, heptyl vinyl ketone, 3-octene-2-one, and expecially acrolein.
  • reaction conditions such as temperature and pressure and the proportions of the reacting substances and the residence time in a given case to a certain extent are dependent upon each other according to the type of reacting substances and the type of catalyst.
  • the reaction is carried out at a temperature between 250° and 550° C. In most cases there are preferred temperatures between 300° and 500° C., especially between 350° and 450° C. It is advantageous to work at pressures of about 1 to 4 bar. However, there can also be used lower or higher pressures although it is suitable not to substantially deviate from this pressure range since it permits the use of simple apparatus.
  • the proportions of cycloalkanone or cycloalkenone to oxo compound (II) can be selected substantially at random, both stoichiometric as well as under or over stoichiometric being usable. Generally, it is advantageous to add about 0.5 to 10 moles of oxo compound per mole of cycloalkanone or cycloalkenone. Preferably there are used about 1 to 5 moles, especially 2 to 4 moles of oxo compound (II) per mole of cycloalkanone or cycloalkenone.
  • the ammonia can be present in the reaction in substantially any proportions from under stoichiometric to over stoichiometric. In most cases it is suitable to have present at least 0.5 mole of ammonia per mole of cycloalkanone or cycloalkenone, however, there can be as much as about 100 moles of ammonia per mole of cycloalkanone or cycloalkenone.
  • the reaction takes place in the gas phase. It can be expedient to dilute the gases of cycloalkanone or cycloalkenone, oxo compound and ammonia with inert gases.
  • inert gases there can be employed, for example, steam, air and especially nitrogen.
  • inert gases there can be employed, for example, steam, air and especially nitrogen.
  • catalysts there can be employed those which have a dehydrating and dehydrogenating action.
  • these include the catalysts described in Hydrocarbon Processing, Vol. 47 (1968) pages 103 to 107 which are aluminum compounds such as aluminum oxide and aluminum silicate, optionally with addition of other metal oxides and fluorides.
  • the entire disclosure of the Hydrocarbon Processing article is hereby incorporated by reference and relied upon.
  • These catalysts are prepared by treating with oxygen at temperatures of 550° to 1200° C. compounds of the elements Al, F and O which compounds also contain at least one element of the second, third or fourth groups of the periodic system (German Offenlegungsschrift No. 2 151 417 and related Beschke U.S. Pat. No. 3,898,177) or at least two elements of the second, fourth, fifth or sixth groups of the periodic system (German Offenlegungsschrift No. 2 224 160 and related Beschke U.S. Pat. No. 3,960,766) or at least one element of the second main group of the periodic system (German Offenlegungsschrift No. 2 239 801 and related Beschke U.S. Pat. No. 3,971,542).
  • the catalysts are used in a fixed bed or preferably in a fluidized bed.
  • Beschke U.S. Pat. No. 3,898,177 describes the catalyst in claim 1 as consisting essentially of oxygen containing compounds of Al, F, at least one of the elements B and Si and at least one element from the second and fourth groups of the periodic system selected from the group consisting of Mg, Ba, Zn, Sn and Zr, said catalyst having been prepared by heating in the presence of oxygen at a temperature of 600° to 800° C.:
  • a compound of fluorine said fluorine having been added as ammonium fluoride, ammonium hydrogen fluoride, hydrogen fluoride, fluoboric acid, fluosilicic acid, boron trifluoride, magnesium fluoborate, magnesium fluosilicate, zinc fluosilicate or barium fluosilicate;
  • Beschke U.S. Pat. No. 3,917,542 in claim 1 describes the catalyst as having been prepared by heating at 600° to 800° C. In the presence of gaseous oxygen, (1) aluminum metal, aluminum oxide or a compound of aluminum convertible to the oxide upon heating with gaseous oxygen at 600° to 800° C., (2) ammonium fluoride, hydrogen fluoride or a fluoride of an element of the second main group of the periodic system and (3) at least one element of the second main group of the periodic system, the oxide of said element or a compound of said element convertible to the oxide in the presence of gaseous oxygen at a temperature of 600° to 800° C., said catalyst consisting essentially of the elements Al, F, O and the element of the second main group of the periodic system.
  • Beschke U.S. Pat. No. 3,960,766 in claim 1 describes the catalyst as consisting essentially of the product obtained by treating with oxygen at a temperature of 550° to 1200° C. compounds of the elements Al, F and O and at least two other elements selected from the second, fourth, fifth and sixth groups of the periodic system, said two other elements being selected from the group consisting of Mg, Ba, Zr, Sn, Ti, P, Ta, Sb and S, the ratios of the elements being Al to F of between 1000 to 10 and 1000 to 800 and of Al to the elements of the second, fourth, fifth and sixth groups being between 1000 to 5 and 1000 to 2000.
  • the working up of the gas mixture resulting from the reaction can take place in customary manner by washing the gases with a liquid, especially water or methanol and by further separation by means of extraction and distillation.
  • a liquid especially water or methanol
  • FIGURE of the drawing is a schematic illustration of an apparatus suitable for carrying out the invention.
  • a tubular reactor 10 provided with cooling and heating devices (not shown).
  • the reactor suitably contains in the middle portion 11 gas distribution plates 30, but in the lower part 12 and the upper part 13 there is free space.
  • the first reaction gas is led into the reactor from below through line 14 and so regulated that the catalyst in the reactor forms a fluidized bed.
  • the other reactant gases are led through line 15 into the fluidized bed.
  • the reaction mixture is drawn off from the reactor in the upper part thereof through the line 16.
  • a portion of the catalyst is always transported via line 17 from the reactor 10 to a regenerator 20.
  • This regenerator also is advantageously constructed similar to the reactor 10.
  • the regenerator also suitably contains gas distribution plates 32 in the middle portion but there is free space in the lower portion 22 and in the upper portion 23.
  • the oxygen or oxygen containing gas is led into the regenerator 20 from below through line 24.
  • the gas flow is so regulated that the catalyst present in the regenerator forms a fluidized bed.
  • the gas escaping from the regenerator via line 25 is discarded.
  • a portion of the catalyst is continuously relieved from the regenerator 20 via line 26 into the reactor 10.
  • the process can comprise, consist essentially of or consist of the steps set forth and the materials can comprise, consist essentially of or consist of those set forth.
  • Reactor 10 and regenerator 20 were used the apparatus of the drawing (also disclosed in German OS No. 2 449 340 and Beschke U.S. application Ser. No. 622,488).
  • Reactor 10 and regenerator 20 consisted of tubes 70 mm wide which had in their lower portions a free space 12 or 22 which was 200 mm high; thereover at intervals of 50 mm there were provided 40 wire screens with meshes of 5 mm (30 and 32) each in the spaces 11 and 21.
  • free spaces 13 and 23 having a height of 600 mm and a width of up to 160 mm.
  • the reactor contained 2.0 kg of catalyst which was produced according to Beschke U.S. Pat. No. 3,960,766 Example 1a (and German Offenlegungsschrift No. 2 224 160) from aluminum oxide, magnesium nitrate and titanium tetrafluoride and had an atomic ratio of aluminum to magnesium to titanium to fluorine of 1000:25:25:100.
  • the catalyst had a particle size between 0.4 and 1.0 mm.
  • the temperature in the reactor was held at 440° C.
  • the reaction mixture leaving via line 16 and which was free from acrolein and cyclododecanone was led at a temperature of 250° C.
  • the regenerator 20 contained an additional 2.0 kg of the catalyst. There were introduced into the regenerator from below via line 24 hourly 3000 normal liters of air. The temperature in the regenerator was held at 440° C. In a steady stream there were transferred hourly from the reactor to the regenerator 1.4 kg of catalyst and likewise there were returned 1.4 kg of catalyst from the regenerator to the reactor.
  • the cyclododecanone reaction was 98%. There were recovered hourly 1895 grams of 2,3-cyclododecenopyridine, 378 grams of pyridine and 1164 grams of 3-methyl pyridine as well as 25 grams of unreacted cyclododecanone. This corresponds to a yield of cyclododecenopyridine of 88.6%, based on the reacted cyclododecanone as well as 12.5% of pyridine and 32.9% of 3-methyl pyridine based on the acrolein added.
  • the 2,3-cyclododecenopyridine had a boiling point of 141° to 144° C. at 5 mbar. Its hydrochloride had a melting point (decomposition point) of 220° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)

Abstract

2,3-Cycloalkenopyridines of the formula ##STR1## are prepared by reacting a cycloalkanone or cycloalkenone of the formula ##STR2## with an oxo compound of the formula ##STR3## where Z is an aliphatic carbon chain which is unsubstituted or has hydrocarbon substituents and R1, R2 and R3 are hydrogen or lower alkyl groups and ammonia in the presence of a dehydrating and dehydrogenating catalyst at a temperature of about 250° to 550° C.

Description

BACKGROUND OF THE INVENTION
The invention is directed to a process for the production of 2,3-cycloalkenopyridines by the catalytic reaction of a cycloalkanone or cycloalkenone with an aliphatic oxo compound at elevated temperature. The 2,3-cycloalkenopyridines are important intermediate products for the production of medicines, plant protective agents and synthetic resins.
It is known to produce 2,3-cyclohexenopyridine by the catalytic dehydrogenation of decahydroquinoline (Berichte Vol. 67 (1934) pages 1715 to 1729). The yield is merely 36%. It is already known to produce 2,3-cyclopentenpyridine, 2,3-cyclohexenopyridine and 2,3-cycloheptenopyridine from the corresponding cycloalkanones (Annalen Vol. 478 (1939) pages 176 to 196, Helv. Chem. Acta Vol. 28 (1945) pages 1677 to 1683), in each using 4 intermediate steps. The disadvantage of these processes is that they are very expensive and the highest yield is 40%.
Furthermore, it is known to produce 2,3-cycloalkenopyridine by reaction of cycloalkanones with 3-aminoacroleins in the liquid phase at 120° C. using triethylamine and piperidine acetate as catalyst (Tetrahedron Letters No. 38 (1970) pages 3291 to 3294). This process requires as the starting materials the relatively difficulty accessible aminoacroleins. Besides despite 24 hours reaction time the yields of the desired cycloalkenopyridines are only 30 to 60%.
SUMMARY OF THE INVENTION
There has now been found a process for the production of 2,3-cycloalkenopyridines by the catalytic reaction of a cycloalkanone or cycloalkenone with an aliphatic oxo compound at elevated temperature wherein the cycloalkanone or cycloalkenone is reacted with an aliphatic oxo compound which has an unsaturated carbon to carbon double bond on the carbon atoms adjacent to the oxo group in the gas phase and with ammonia and in the presence of a dehydrating and dehydrogenating catalyst at a temperature of about 250° to 550° C. In this process the cycloalkanone or cycloalkenone is reacted with simple, easily accessible substances. High yields have been produced.
According to the invention (1) a cycloalkenone or preferably a cycloalkanone of the general formula ##STR4## in which Z is an aliphatic carbon atom chain, preferably with 2 to 16 carbon atoms, which in a given case in branched and whose branchings in a given case are closed to a ring or several rings, or especially an aliphatic carbon chain with 3 to 10 carbon atoms, which chain may be branched, e.g., an alkylene group with or without a lower alkyl side chain, methyl being the preferred side chain is reacted (2) with an oxo compound of the general formula ##STR5## in which R1, R2 and R3 are the same or different and are hydrogen or lower alkyl groups with preferably 1 to 6, especially 1 to 2, carbon atoms and in which in a given case the alkyl groups can be branched, and (3) with ammonia to form a compound of the general formula ##STR6## in which Z, R1, R2 and R3 are as defined above. Z is a hydrocarbon group.
As cycloalkanones there can be used for example cyclobutanone, cyclopentadecanone, cyclohexadecanone, cyclooctadecanone, 3,5,5-trimethyl cyclohexanone, camphor, 1-decalone, 2-butyl cyclohexanone, 2-propyl cyclohexanone, 8-ketotricyclodecane, carvone, and especially cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclodecanone, cyclododecanone, 2-methyl cyclohexanone, 3-methyl cyclohexanone, 2,2,4-trimethyl cyclopentanone and menthone. An example of a cycloalkenone is isophorone.
Suitable oxo compounds are for example, methacrolein, crotonaldehyde, methyl vinyl ketone, ethyl vinyl ketone, 3-penten-2-one, hexyl vinyl ketone, heptyl vinyl ketone, 3-octene-2-one, and expecially acrolein.
The reaction conditions such as temperature and pressure and the proportions of the reacting substances and the residence time in a given case to a certain extent are dependent upon each other according to the type of reacting substances and the type of catalyst.
In general, the reaction is carried out at a temperature between 250° and 550° C. In most cases there are preferred temperatures between 300° and 500° C., especially between 350° and 450° C. It is advantageous to work at pressures of about 1 to 4 bar. However, there can also be used lower or higher pressures although it is suitable not to substantially deviate from this pressure range since it permits the use of simple apparatus.
The proportions of cycloalkanone or cycloalkenone to oxo compound (II) can be selected substantially at random, both stoichiometric as well as under or over stoichiometric being usable. Generally, it is advantageous to add about 0.5 to 10 moles of oxo compound per mole of cycloalkanone or cycloalkenone. Preferably there are used about 1 to 5 moles, especially 2 to 4 moles of oxo compound (II) per mole of cycloalkanone or cycloalkenone.
The ammonia can be present in the reaction in substantially any proportions from under stoichiometric to over stoichiometric. In most cases it is suitable to have present at least 0.5 mole of ammonia per mole of cycloalkanone or cycloalkenone, however, there can be as much as about 100 moles of ammonia per mole of cycloalkanone or cycloalkenone. Advantageously, there are employed about 1 to 20 moles of ammonia, preferably 2 to 15 moles of ammonia, especially 3 to 12 moles of ammonia, per mole of cycloalkanone or cycloalkenone.
The reaction takes place in the gas phase. It can be expedient to dilute the gases of cycloalkanone or cycloalkenone, oxo compound and ammonia with inert gases. As inert gases there can be employed, for example, steam, air and especially nitrogen. Generally, it is expedient to use in all not more than about 20 moles of inert gas per mole of cycloalkanone or cycloalkenone. Preferably, there are used about 0.5 to 10 moles, particularly 1 to 5 moles of inert gas per mole of cycloalkanone or cycloalkenone.
As catalysts there can be employed those which have a dehydrating and dehydrogenating action. For example, these include the catalysts described in Hydrocarbon Processing, Vol. 47 (1968) pages 103 to 107 which are aluminum compounds such as aluminum oxide and aluminum silicate, optionally with addition of other metal oxides and fluorides. The entire disclosure of the Hydrocarbon Processing article is hereby incorporated by reference and relied upon.
With advantage there is used in the process catalysts produced according to German Offenlegungsschrift No. 2 151 417 and related Beschke U.S. Pat. No. 3,898,177; according to German OS No. 2 224 160 and related Beschke U.S. Pat. No. 3,960,766; and according to German OS No. 2 239 801 and related Beschke U.S. Pat. No. 3,917,542. The entire disclosure of Beschke Pat. Nos. 3,898,177; 3,917,542 and 3,960,766 are hereby incorporated by reference and relied upon.
These catalysts are prepared by treating with oxygen at temperatures of 550° to 1200° C. compounds of the elements Al, F and O which compounds also contain at least one element of the second, third or fourth groups of the periodic system (German Offenlegungsschrift No. 2 151 417 and related Beschke U.S. Pat. No. 3,898,177) or at least two elements of the second, fourth, fifth or sixth groups of the periodic system (German Offenlegungsschrift No. 2 224 160 and related Beschke U.S. Pat. No. 3,960,766) or at least one element of the second main group of the periodic system (German Offenlegungsschrift No. 2 239 801 and related Beschke U.S. Pat. No. 3,971,542). The catalysts are used in a fixed bed or preferably in a fluidized bed.
Beschke U.S. Pat. No. 3,898,177 describes the catalyst in claim 1 as consisting essentially of oxygen containing compounds of Al, F, at least one of the elements B and Si and at least one element from the second and fourth groups of the periodic system selected from the group consisting of Mg, Ba, Zn, Sn and Zr, said catalyst having been prepared by heating in the presence of oxygen at a temperature of 600° to 800° C.:
1. aluminum, aluminum oxide or an aluminum compound convertible to the oxide at said temperature;
2. a compound of fluorine, said fluorine having been added as ammonium fluoride, ammonium hydrogen fluoride, hydrogen fluoride, fluoboric acid, fluosilicic acid, boron trifluoride, magnesium fluoborate, magnesium fluosilicate, zinc fluosilicate or barium fluosilicate;
3. boron, silicon, boric oxide, silica or a compound of boron or silica convertible to the oxide at said temperature; and,
4. magnesium, zinc, tin, zirconium, magnesium oxide, zinc oxide, tin oxide or a compound of zirconium or barium convertible to the oxide at said temperature, the atomic ratio of Al to F being from 1000:25 to 1000:800 and the atomic ratio of Al to the total of (3) and (4) being from 1000:5 to 1000:200, the atomic ratio of the total of boron and silicon to the other element from the second and fourth groups being between 1 to 10 and 10 to 1.
Beschke U.S. Pat. No. 3,917,542 in claim 1 describes the catalyst as having been prepared by heating at 600° to 800° C. In the presence of gaseous oxygen, (1) aluminum metal, aluminum oxide or a compound of aluminum convertible to the oxide upon heating with gaseous oxygen at 600° to 800° C., (2) ammonium fluoride, hydrogen fluoride or a fluoride of an element of the second main group of the periodic system and (3) at least one element of the second main group of the periodic system, the oxide of said element or a compound of said element convertible to the oxide in the presence of gaseous oxygen at a temperature of 600° to 800° C., said catalyst consisting essentially of the elements Al, F, O and the element of the second main group of the periodic system.
Beschke U.S. Pat. No. 3,960,766 in claim 1 describes the catalyst as consisting essentially of the product obtained by treating with oxygen at a temperature of 550° to 1200° C. compounds of the elements Al, F and O and at least two other elements selected from the second, fourth, fifth and sixth groups of the periodic system, said two other elements being selected from the group consisting of Mg, Ba, Zr, Sn, Ti, P, Ta, Sb and S, the ratios of the elements being Al to F of between 1000 to 10 and 1000 to 800 and of Al to the elements of the second, fourth, fifth and sixth groups being between 1000 to 5 and 1000 to 2000.
Especially advantageous is a procedure using the apparatus and method of German OS No. 2 449 340 and related Beschke U.S. application Ser. No. 622,488 filed Oct. 15, 1975 in which instead of the reactants mentioned in the German OS No. 2 449 340 and Beschke cycloalkanone or cycloalkenone and oxo compound are fed into the reactor separate from the ammonia. Generally, the residence time in the reactor is between 0.2 and 5.0 seconds. The entire disclosure of the Beschke U.S. application Ser. No. 622,488 is hereby incorporated by reference and relied upon.
The working up of the gas mixture resulting from the reaction can take place in customary manner by washing the gases with a liquid, especially water or methanol and by further separation by means of extraction and distillation. With especial advantage there is employed the procedure of German OS No. 2 554 946 and related Beschke U.S. application Ser. No. 748,041 filed Dec. 6, 1976 in which the gas mixture is not washed but cooled and as a result partially condensed in such manner that any possible excess ammonia remains in the residual gas and with this is directly recycled.
BRIEF DESCRIPTION OF THE DRAWINGS
The single FIGURE of the drawing is a schematic illustration of an apparatus suitable for carrying out the invention.
Referring more specifically to the drawing, there is used a tubular reactor 10 provided with cooling and heating devices (not shown). The reactor suitably contains in the middle portion 11 gas distribution plates 30, but in the lower part 12 and the upper part 13 there is free space. The first reaction gas is led into the reactor from below through line 14 and so regulated that the catalyst in the reactor forms a fluidized bed. The other reactant gases are led through line 15 into the fluidized bed. The reaction mixture is drawn off from the reactor in the upper part thereof through the line 16. A portion of the catalyst is always transported via line 17 from the reactor 10 to a regenerator 20. This regenerator also is advantageously constructed similar to the reactor 10. The regenerator also suitably contains gas distribution plates 32 in the middle portion but there is free space in the lower portion 22 and in the upper portion 23. The oxygen or oxygen containing gas is led into the regenerator 20 from below through line 24. The gas flow is so regulated that the catalyst present in the regenerator forms a fluidized bed. The gas escaping from the regenerator via line 25 is discarded. A portion of the catalyst is continuously relieved from the regenerator 20 via line 26 into the reactor 10.
Unless otherwise indicated all parts and percentages are by weight.
The process can comprise, consist essentially of or consist of the steps set forth and the materials can comprise, consist essentially of or consist of those set forth.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Example 1
There was used the apparatus of the drawing (also disclosed in German OS No. 2 449 340 and Beschke U.S. application Ser. No. 622,488). Reactor 10 and regenerator 20 consisted of tubes 70 mm wide which had in their lower portions a free space 12 or 22 which was 200 mm high; thereover at intervals of 50 mm there were provided 40 wire screens with meshes of 5 mm (30 and 32) each in the spaces 11 and 21. There were provided above free spaces 13 and 23 having a height of 600 mm and a width of up to 160 mm.
There were led into the reactor 10 in gaseous form in uniform flow hourly from below via line 14 a gas mixture of 1500 normal liters (i.e., measured at standard pressure and temperature) of nitrogen and 2150 normal liters of ammonia. In a vaporizer there was prepared hourly a gas mixture from 2130 grams of acrolein and 325 normal liters of nitrogen. In a further vaporizer there was prepared a similar gaseous mixture from 1820 grams of cyclododecanone and 325 normal liters of nitrogen. These gaseous mixtures were combined and from the side via line 15 were led into the fluidized layer 130 mm above the bottom of the reactor at a temperature of 250° C.
The reactor contained 2.0 kg of catalyst which was produced according to Beschke U.S. Pat. No. 3,960,766 Example 1a (and German Offenlegungsschrift No. 2 224 160) from aluminum oxide, magnesium nitrate and titanium tetrafluoride and had an atomic ratio of aluminum to magnesium to titanium to fluorine of 1000:25:25:100. The catalyst had a particle size between 0.4 and 1.0 mm. The temperature in the reactor was held at 440° C. The reaction mixture leaving via line 16 and which was free from acrolein and cyclododecanone was led at a temperature of 250° C. into a gas washing apparatus in which the 2,3-cyclododecenopyridine and the pyridine and 3-methyl pyridine byproducts were washed out by means of methanol. The remaining residual gas of ammonia and nitrogen was recycled into the reactor.
The regenerator 20 contained an additional 2.0 kg of the catalyst. There were introduced into the regenerator from below via line 24 hourly 3000 normal liters of air. The temperature in the regenerator was held at 440° C. In a steady stream there were transferred hourly from the reactor to the regenerator 1.4 kg of catalyst and likewise there were returned 1.4 kg of catalyst from the regenerator to the reactor.
The cyclododecanone reaction was 98%. There were recovered hourly 1895 grams of 2,3-cyclododecenopyridine, 378 grams of pyridine and 1164 grams of 3-methyl pyridine as well as 25 grams of unreacted cyclododecanone. This corresponds to a yield of cyclododecenopyridine of 88.6%, based on the reacted cyclododecanone as well as 12.5% of pyridine and 32.9% of 3-methyl pyridine based on the acrolein added. The 2,3-cyclododecenopyridine had a boiling point of 141° to 144° C. at 5 mbar. Its hydrochloride had a melting point (decomposition point) of 220° C.
In the following examples, there was used the same procedure as in Example 1.
Example 2 
______________________________________                                    
Starting Materials:                                                       
               Cycloheptanone, acrolein and                               
               ammonia in the molar ratios of                             
               1:2.8:11.2                                                 
Catalyst:      As in Example 1                                            
Reaction Temperature:                                                     
               430° C.                                             
Reaction:      100% of the cycloheptanone                                 
Product:       2,3-cycloheptenopyridine                                   
               B.P. 104 to 114° C. at 17 mbar,                     
               M.P. of the hydrochloride 158° C.                   
Yield:         69% based on the reacted                                   
               cycloheptanone                                             
Byproducts:    11% pyridine and 30% 3-methyl                              
               pyridine based on the acrolein                             
               added                                                      
______________________________________
Example 3 
______________________________________                                    
Starting Materials:                                                       
                Cyclopentanone, acrolein and                              
                ammonia in the molar ratios of                            
                1:2.8:11.2                                                
Catalyst:       As in Example 1                                           
Reaction Temperature:                                                     
                420° C.                                            
Reaction:       100% of the cyclopentanone                                
Product:        2,3-cyclopentenopyridine,                                 
                B.P. 78 to 83° C. at 17 mbar, M.P.                 
                (decomposition point) of the                              
                hydrochloride 153° C.                              
Yield:          64% based on the reacted cyclo-                           
                pentanone                                                 
Byproducts:     12% pyridine and 31% 3-methyl                             
                pyridine based on the acrolein                            
                added                                                     
______________________________________
EXAMPLE 4 
______________________________________                                    
Starting Materials:                                                       
                3-methyl-5-dimethylcyclohexanone,                         
                acrolein and ammonia in the                               
                molar ratios of 1:3:12                                    
Catalyst:       As in Example 1                                           
Reaction Temperature:                                                     
                440° C.                                            
Reaction:       100% of the 3-methyl-5-dimethyl-                          
                cyclohexanone                                             
Product:        Isomeric mixture of 60% 5-methyl-                         
                7-dimethyl-5,6,7,8-tetrahydro-                            
                quinoline and 40% 5-dimethyl-7-                           
                methyl-5,6,7,8-tetrahydroquinoline                        
                B.P. 115 to 120° C. at 17 mbar                     
Yield:          A total of 71% based on the                               
                reacted cyclohexanone                                     
Byproducts:     12% pyridine and 29% 3-methyl                             
                pyridine based on the acrolein                            
                added                                                     
______________________________________
Example 5 
______________________________________                                    
Starting Materials:                                                       
                Cyclohexanone, acrolein and                               
                ammonia in the molar ratios of                            
                1:2.9:9.6                                                 
Catalyst:       According to Beschke U.S.                                 
                Pat. No. 3,898,177 Example 5 (and                         
                German OS 2 151 417) from                                 
                aluminum oxide, magnesium                                 
                nitrate and fluosilicic acid,                             
                atomic ratio aluminum to                                  
                magnesium to silicon to fluorine                          
                of 1000:24:25:156                                         
Reaction Temperature:                                                     
                400° C.                                            
Reaction:       94% of the cyclohexanone                                  
Product:        2,3-cyclohexenopyridine, B.P.                             
                95 to 99° C. at 17 mbar, M.P. of                   
                the hydrochloride 134° C.                          
Yield:          53% based on the reacted                                  
                cyclohexanone                                             
Byproducts:     15% pyridine and 25% 3-methyl                             
                pyridine based on the acrolein                            
                added                                                     
______________________________________
Example 6 
______________________________________                                    
Starting Materials:                                                       
                Cyclohexanone, acrolein and                               
                ammonia in the molar ratios                               
                of 1:2.4:6                                                
Catalyst:       According to Beschke U.S.                                 
                Pat. No. 3,917,542 Example 1 (and                         
                German OS 2 239 801) from                                 
                aluminum oxide, magnesium nitrate                         
                and ammonium hydrogen fluoride                            
                in the atomic ratio aluminum to                           
                magnesium to fluorine of                                  
                1000:25:50                                                
Reaction Temperature:                                                     
                370° C.                                            
Reaction:       92% of the cyclohexanone                                  
Product:        2,3-cyclohexenopyridine, B.P.                             
                95 to 99° C. at 17 mbar, M.P. of the               
                hydrochloride 134° C.                              
Yield:          58% based on the reacted                                  
                cyclohexanone                                             
Byproducts:     14% pyridine and 21% 3-methyl                             
                pyridine based on the acrolein                            
                added                                                     
______________________________________
Example 7 
______________________________________                                    
Starting Materials:                                                       
               Cyclododecanone, crotonaldehyde                            
               and ammonia in the molar ratios                            
               of 1:2:8                                                   
Catalyst:      As in Example 1                                            
Reaction Temperature:                                                     
               430° C.                                             
Reaction:      100% of the cyclododecanone                                
Product:       2,3-cyclododeceno-4-methyl                                 
               pyridine, B.P. 172 to 183° C.                       
               at 6 mbar                                                  
Yield:         37% based on the reacted                                   
               cyclododecanone                                            
Byproducts:    8% pyridine, 11% 2-methyl pyridine                         
               and 21% 4-methyl pyridine based                            
               on the crotonaldehyde added                                
______________________________________
Example 8 
______________________________________                                    
Starting Materials:                                                       
                Cyclohexanone, methacrolein                               
                and ammonia in the molar ratios                           
                of 1:3:6                                                  
Catalyst:       As in Example 1                                           
Reaction Temperature:                                                     
                420° C.                                            
Reaction:       100% of the cyclohexanone                                 
Product:        2,3-cyclohexeno-5-methyl pyridine,                        
                B.P. 96 to 102° C. at 13 mbar                      
Yield:          64% based on the reacted                                  
                cyclohexanone                                             
Byproducts:     5% pyridine and 27% 3,5-dimethyl                          
                pyridine based on the methacrolein                        
                added                                                     
______________________________________
Example 9 
______________________________________                                    
Starting Materials:                                                       
                 Cyclododecanone, methyl vinyl                            
                 ketone and ammonia in the molar                          
                 ratios 1:2.6:10.4                                        
Catalyst:        As in Example 1                                          
Reaction Temperature:                                                     
                 420° C.                                           
Reaction:        100% of the cyclododecanone                              
Product:         2,3-cyclododeceno-6-methyl                               
                 pyridine, B.P. 146 to 158° C.                     
                 at 3 mbar                                                
Yield:           73% based on the reacted cyclo-                          
                 dodecanone                                               
Byproducts:      27% collidine mixture based on                           
                 the methyl vinyl ketone added                            
______________________________________
Example 10 
______________________________________                                    
Starting Materials:                                                       
                 Cyclohexanone, acrolein and                              
                 ammonia in the molar ratio                               
                 1:1:4                                                    
Catalyst:        Aluminum silicate consisting                             
                 of 87% SiO.sub.2 and 13% Al.sub.2 O.sub.3,               
                 BET surface area 500 m.sup.2 /g,                         
                 particle size 0.4 to 1.0 mm,                             
                 pore volume 0.75 cm.sup.3 /g, pore                       
                 diameter 60 angstroms                                    
Reaction Temperature:                                                     
                 440° C.                                           
Reaction:        100% of the cyclohexanone                                
Product:         2,3-cyclohexenopyridine, B.P.                            
                 95 to 99° C. at 17 mbar, M.P. of                  
                 the hydrochloride 134° C.                         
Yield:           38% based on the reacted cyclo-                          
                 hexanone                                                 
Byproducts:      13% pyridine and 34% 3-methyl                            
                 pyridine based on the acrolein                           
                 added                                                    
______________________________________
Example 11 
______________________________________                                    
Starting Materials:                                                       
               2,2,4(2,4,4)-trimethylcyclo-                               
               pentanone (TMCP-on of the firm                             
               VEBA), acrolein and ammonia in                             
               the molar ratios 1:3:12                                    
Catalyst:      As in Example 1                                            
Reaction Temperature:                                                     
               420° C.                                             
Reaction:      100% of the trimethylcyclopentanone                        
Product:       Mixture of 1'-dimethyl-3'-methyl-                          
               2,3-cyclopentenopyridine and                               
               1'-methyl-3'-dimethyl-2,3-                                 
               cyclopentenopyridine, B.P. 88 to                           
               103° C. at 14 mbar                                  
Yield:         37% based on the reacted                                   
               trimethylcyclopentanone                                    
Byproducts:    31% pyridine and 36% 3-methyl-                             
               pyridine based on the acrolein                             
               added                                                      
______________________________________
EXAMPLE 12 
______________________________________                                    
Starting Materials:                                                       
                 Isophorone (3,5,5-trimethyl-                             
                 2-cyclohexenone), acrolein and                           
                 ammonia in the molar ratios of                           
                 1:3:10                                                   
Catalyst:        As in Example 1                                          
Reaction Temperature:                                                     
                 420° C.                                           
Reaction:        94% of the isophorone                                    
Product:         (a) 5-dimethyl-7-methyl-5,6-                             
                 dihydroquinoline                                         
                 (b) 5-dimethyl-7-methyl-5,6,7,8-                         
                 tetrahydroquinoline                                      
                 (c) 5,7-dimethyl quinoline                               
Yield:           55% ((a) 5%, (b) 16%, (c) 34%)                           
                 based on the reacted isophorone                          
Byproducts:      16% pyridine and 30% 3-methyl                            
                 pyridine based on the acrolein                           
                 added                                                    
______________________________________

Claims (24)

What is claimed is:
1. In a process for the production of a 2,3-cycloalkenopyridine of the formula ##STR7## where Z is an unsubstituted or 1 to 6 carbon atoms alkyl substituted aliphatic carbon chain having a 2 to 16 carbon atoms and R1, R2 and R3 are hydrogen or 1 to 6 carbon atom alkyl group comprising the step of catalytically reacting a cycloalkanone of the formula ##STR8## or isophorone with an oxo compound having the formula ##STR9## and ammonia in the gas phase at a temperature from about 250° to 550° C., the improvement comprising carrying out the reaction in the presence of a dehydrating and dehydrogenating catalyst which is (1) a catalyst consisting essentially of oxygen containing compounds of Al, F at least one of the elements B and Si and at least one element from the second and fourth groups of the periodic system selected from the group consisting of Mg, Ba, Zn, Sn and Zr, said catalyst having been prepared by heating in the presence of oxygen at a temperature of 600° to 800° C.;
1. aluminum, aluminum oxide or an aluminum compound convertible to the oxide at a said temperature,
2. a compound of fluorine, said fluorine having been added as ammonium fluoride, ammonium hydrogen fluoride, hydrogen fluoride, fluoboric acid, fluosilicic acid, boron trifluoride, magnesium fluoborate, magnesium fluosilicate, zinc fluosilicate or barium fluosilicate,
3. boron, silicon, boric oxide, silica or a compound of boron or silica convertible to the oxide at said temperature and
4. magnesium, zinc, tin, zirconium, magnesium oxide, zinc oxide, tin oxide or a compound of zirconium or barium convertible to the oxide at said temperature, the atomic ratio of Al to F being from 1000:25 of 1000:800 and the atomic ratio of Al to the total of (3) and (4) being from 1000:5 to 1000:200, the atomic ratio of the total of boron and silicon to the other element from the second and fourth groups being between 1 to 10 and 10 to 1 or (2) a catalyst having been prepared by heating at 600° to 800° C. in the presence of gaseous oxygen (1) aluminum metal, aluminum oxide, or a compound of aluminum convertible to the oxide upon heating with gaseous oxygen at 600° to 800° C., (2) ammonium fluoride, hydrogen fluoride or a fluoride of an element of the second main group of the periodic system and (3) at least one element of the second main group of the periodic system, the oxide of said element or a compound of said element convertible to the oxide in the presence of gaseous oxygen at a temperature of 600° to 800° C., said catalyst consisting essentially of the elements Al, F, O and the element of the second main group of the periodic system or (3) a catalyst consisting essentially of the product obtained by treating with oxygen at a temperature of 550° to 1200° C. compounds of the elements Al, F and O and at least two other elements selected from the second, fourth, fifth and sixth groups of the periodic system, said two other elements being selected from the group consisting of Mg, Ba, Zr, Sn, Ti, P, Ta, Sb and S, the ratios of the elements being Al to F of between 1,000 to 10 and 1,000 to 800 and of Al to the elements of the second, fourth, fifth and sixth groups being between 1,000 to 5 and 1,000 to 200.
2. The process according to claim 1 wherein Z is unsubstituted or has 1 to 3 methyl substituents.
3. The process of claim 2 wherein R1, R2 and R3 are hydrogen or alkyl of 1 to 2 carbon atoms.
4. The process of claim 3 wherein (II) is acrolein.
5. The process of claim 1 wherein (I) is an unsubstituted cycloalkanone of 4 to 18 carbon atoms, trimethylcyclohexanone, 8-ketotricyclodecane, carvone, methyl cyclohexanone, trimethylcyclopentanone, isophorone or menthone and (II) is acrolein, methacrolein, crotonaldehyde, alkyl vinyl ketone having 1 to 2 carbon atoms in the alkyl group and 3-penten-2-one.
6. The process of claim 5 wherein (I) is cyclododecanone, cycloheptanone, cyclopentanone, 3-methyl-5-dimethyl-2-cyclohexanone, cyclohexanone, 2,2,4-trimethylcyclopentanone or isophorone and (II) is acrolein, methacrolein, crotonaldehyde or methyl vinyl ketone.
7. The process of claim 6 wherein (II) is acrolein.
8. The process of claim 5 wherein (I) is an unsubstituted cycloalkanone of 5 to 12 carbon atoms or 3-methyl-5-dimethylcyclohexanone and (II) is acrolein, methacrolein or methyl vinyl ketone.
9. The process of claim 1 wherein the reaction temperature is 300° to 500° C.
10. The process of claim 9 wherein the reaction temperature is 350° to 450° C.
11. The process of claim 9 wherein the catalyst is (1).
12. The process of claim 1 wherein there is used 1 to 5 moles of oxo compound per mole of cycloalkanone or isophorone.
13. The process of claim 12 wherein there is used 1 to 20 moles of ammonia per mole of cycloalkanone or isophorone.
14. The process of claim 13 wherein the reaction is carried out in the presence of an inert gas.
15. The process of claim 14 comprising carrying out the reaction in a fluidized bed and the cycloalkanone or isophorone and oxo compound are added together to the reaction zone separate from the ammonia.
16. The process of claim 1 wherein there is used 0.5 to 10 moles of oxo compound per mole of cycloalkanone or isophorone.
17. The process of claim 16 wherein there is employed 0.5 to 100 moles of ammonia per mole of cycloalkanone or isophorone.
18. The process of claim 17 wherein there is employed 3 to 12 moles of ammonia and 1 to 5 moles of oxo compound per mole of cycloalkanone or isophorone.
19. The process of claim 18 wherein there is used 4 to 12 moles of ammonia per mole of cycloalkanone or isophorone.
20. The process of claim 17 wherein there is used 1 to 10 moles of oxo compound and 4 to 100 per mole of cycloalkanone or isophorone.
21. The process of claim 1 wherein the catalyst is catalyst (1).
22. The process of claim 1 wherein the catalyst is catalyst (2).
23. The process of claim 1 wherein the catalyst is catalyst (3).
US05/830,983 1976-09-03 1977-09-06 Process for the production of 2,3-cycloalkenopyridines Expired - Lifetime US4332940A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2639702A DE2639702C2 (en) 1976-09-03 1976-09-03 Process for the preparation of 2,3-cycloalkenopyridines
DE2639702 1976-09-03

Publications (1)

Publication Number Publication Date
US4332940A true US4332940A (en) 1982-06-01

Family

ID=5987070

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/830,983 Expired - Lifetime US4332940A (en) 1976-09-03 1977-09-06 Process for the production of 2,3-cycloalkenopyridines

Country Status (12)

Country Link
US (1) US4332940A (en)
JP (1) JPS5350173A (en)
BE (1) BE858387A (en)
BR (1) BR7705879A (en)
CA (1) CA1084934A (en)
CH (1) CH631707A5 (en)
DE (1) DE2639702C2 (en)
FR (1) FR2363557A1 (en)
GB (1) GB1550722A (en)
IL (1) IL52884A0 (en)
IT (1) IT1143595B (en)
NL (1) NL181359C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5197266A (en) * 1991-01-22 1993-03-30 Ben Kambeitz Vacuum for combine harvester
CN103539736A (en) * 2013-10-14 2014-01-29 浙江工业大学之江学院工业研究院 Method for synthesis of 2,3-cyclopentenopyridine from glycerin as raw material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2815062B2 (en) * 1988-08-03 1998-10-27 広栄化学工業株式会社 Method for producing cycloalkeno [b] pyridine derivative
WO2011160254A1 (en) * 2010-06-22 2011-12-29 Givaudan Sa Organic compounds

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB633266A (en) 1947-02-12 1949-12-12 Roche Products Ltd Process for the manufacture of 5,6,7,8-tetrahydroisoquinoline
US3898179A (en) * 1973-10-17 1975-08-05 Universal Oil Prod Co Cobalt-and sulfur-containing olefin isomerization process catalyst
US3917542A (en) * 1972-08-12 1975-11-04 Degussa Catalyst for the production of pyridine and 3-methylpyridine
US3960766A (en) * 1972-05-18 1976-06-01 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Catalyst for the production of pyridine and 3-methylpyridine
US4171444A (en) * 1977-08-16 1979-10-16 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for the production of substituted pyridine (C)
US4171445A (en) * 1974-10-17 1979-10-16 Deutsche Gold- Und Siber-Scheideanstalt Vormals Roessler Process for the production of pyridine and 3-methyl pyridine
US4175195A (en) * 1976-09-03 1979-11-20 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for the production of substituted pyridine (A)
US4179576A (en) * 1976-10-27 1979-12-18 Asahi Kasei Kogyo Kabushiki Kaisha Process for preparing pyridine bases

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR875010A (en) * 1939-01-06 1942-09-03 Schering Ag Process for the preparation of heterocyclic compounds of the pyridine series
US3020282A (en) * 1957-07-22 1962-02-06 Reilly Tar & Chem Corp Process of preparing quinoline
US3501479A (en) * 1967-05-19 1970-03-17 American Cyanamid Co Dihydroquinolines and substituted dihydroquinolines and method of preparing the same
BE790121A (en) * 1971-10-15 1973-02-01 Degussa CATALYSTS FOR THE PREPARATION OF PYRIDINE AND 3-METHYLPYRIDINE

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB633266A (en) 1947-02-12 1949-12-12 Roche Products Ltd Process for the manufacture of 5,6,7,8-tetrahydroisoquinoline
US3960766A (en) * 1972-05-18 1976-06-01 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Catalyst for the production of pyridine and 3-methylpyridine
US3917542A (en) * 1972-08-12 1975-11-04 Degussa Catalyst for the production of pyridine and 3-methylpyridine
US3898179A (en) * 1973-10-17 1975-08-05 Universal Oil Prod Co Cobalt-and sulfur-containing olefin isomerization process catalyst
US4171445A (en) * 1974-10-17 1979-10-16 Deutsche Gold- Und Siber-Scheideanstalt Vormals Roessler Process for the production of pyridine and 3-methyl pyridine
US4175195A (en) * 1976-09-03 1979-11-20 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for the production of substituted pyridine (A)
US4179576A (en) * 1976-10-27 1979-12-18 Asahi Kasei Kogyo Kabushiki Kaisha Process for preparing pyridine bases
US4171444A (en) * 1977-08-16 1979-10-16 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Process for the production of substituted pyridine (C)

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Breitmaier et al., "Tetrahedron Letters", No. 38 (1970), pp. 3291-3294. *
Klingsberg Pyridine and Its Derivatives, Part One, Interscience, N.Y., pp. 498-500; 508 (1960). *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5197266A (en) * 1991-01-22 1993-03-30 Ben Kambeitz Vacuum for combine harvester
CN103539736A (en) * 2013-10-14 2014-01-29 浙江工业大学之江学院工业研究院 Method for synthesis of 2,3-cyclopentenopyridine from glycerin as raw material
CN103539736B (en) * 2013-10-14 2015-05-13 浙江工业大学之江学院工业研究院 Method for synthesis of 2,3-cyclopentenopyridine from glycerin as raw material

Also Published As

Publication number Publication date
DE2639702A1 (en) 1978-03-16
DE2639702C2 (en) 1984-03-08
FR2363557A1 (en) 1978-03-31
BR7705879A (en) 1978-06-27
CH631707A5 (en) 1982-08-31
NL181359C (en) 1987-08-03
NL7709707A (en) 1978-03-07
JPS5350173A (en) 1978-05-08
IT1143595B (en) 1986-10-22
BE858387A (en) 1978-03-02
FR2363557B1 (en) 1982-07-16
CA1084934A (en) 1980-09-02
JPS6313988B2 (en) 1988-03-29
NL181359B (en) 1987-03-02
IL52884A0 (en) 1977-11-30
GB1550722A (en) 1979-08-22

Similar Documents

Publication Publication Date Title
US4429132A (en) Production of 3-trichloromethyl- and 3-trifluoromethyl-pyridines
US4175195A (en) Process for the production of substituted pyridine (A)
EP0442087B1 (en) Process for preparing saturated fluorinated hydrocarbons without chlorine
US4332940A (en) Process for the production of 2,3-cycloalkenopyridines
EP2953920B1 (en) Process for the isomerisation of an exo double bond
US4275238A (en) Process for the preparation of cyclopropylmethyl-n-propylamine
JPS5811846B2 (en) Resorcinol Resorcinol
US2549520A (en) Preparation of substituted cyclic ketones
US4169951A (en) Process for the production of substituted pyridine (b)
US6037501A (en) Process for producing fluorene or its derivatives
US2746993A (en) Dehydrogenation of alcohols
US6005147A (en) Method of producing 3, 5, 5-trimethylcyclohexa-3-ene-1-one(β-isophorone) by the isomerization of 3, 5, 5-trimethylcyclohexa-2-ene-1-(α-isophorone)
US2634269A (en) Process for manufacturing caprolactam
EP0057890B1 (en) Process for the preparation of pyridines or pyrroles from alpha, omega-dinitriles
JPS6356214B2 (en)
US4508896A (en) Process for the simultaneous production of 2-(2-aminoalkoxy)alkanol and morpholine
US2876255A (en) Preparation of bromo acids and esters
CA1084932A (en) Producing pyridines aromatically and heteroaromatically substituted in the 2 and 6 positions
CA1088941A (en) Process for producing bis(cycloalkeno)-pyridines
US3020281A (en) Method of preparing quinoline
US4215063A (en) Oxidation catalyst and use in the production of anthraquinone
US3085121A (en) Process for the production of 1, 3-cyclohexadiene
DE69318738T2 (en) Catalytic synthesis of alkylmorpholinones
US4237299A (en) Process for the recovery of pyridine and 3-methylpyridine
US4028362A (en) Process for the preparation of quinolines

Legal Events

Date Code Title Description
AS Assignment

Owner name: DEUTSCHE GOLD-UND SILBER-SCHEIDEANSTALT VORMALS RO

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:BESCHKE, HELMUT;FRIEDRICH, HEINZ;OFFERMANNS, HERIBERT;REEL/FRAME:003841/0640;SIGNING DATES FROM 19771018 TO 19771020

STCF Information on status: patent grant

Free format text: PATENTED CASE